Cellulose-morpholinium derivative composition and process



Patented Dec. 30, 1952 1 UNITED STATS CELLULO SE-MORPHOLINIUM DERIVATIVE COMPOSITION AND PROCESS No Drawing. Application January 16, 1950, serial No. 138,940

15 Claims. (oi. ace-n2) 'Ihe present. invention relates to improvements inv the processing of refined chemical pulp and more'p-articularly to the manufacture of cellulose pulp for use in the manufacture of regenerated through orifices of proper dimension into coagulating baths of acid or acid-salt mixture.

In my copending application Serial No. 56,668, filed October 26, 1948, now Patent No. 2,495,833

cellulose filament and/or films by the viscose 5 issued January 31, 1950 I have disclosed that process. certain surfaceactive morpholinium or thiom'or- Cellulose to be converted into rayon or celiopholinium derivatives may be advantageously phane film by the viscose process is usually supincorporated in the coagulating bath or in the pliedto the manufacturer of such materials in viscose solution being extruded into the coagulatthe form of refined cellulose fibers matted toing bath; whereby encrustation of the orifice is getherinto thick sheets. Much of the cellulose avoided, with consequent improvement in quality so provided is prepared by sulfite digestion of of product and facility of operation; Wood pulp whereby the non-cellulosic portion of In accordance with the present invention I find the wood is dissolved away leaving the cellulose it advantageous to incorporate the said morphofibers which may be further purified and bleached linium or thiomorpholinium derivatives at an before felting into the sheet form usually delivearlier stage in the process by which cellulose is ered to manufacturers of regenerated cellulosic converted to regenerated'cellulose,preferably in products under the designation refined chemical the preparation of the refined chemical pulp it pulp. self, prior to any of the steps'normally asso- It is the object of the present invention to prociated with the viscose process. The compounds vide a specially treated refined cellulose pulp. which are incorporated into refined chemical pulp It is a more particular object of the invention in accordance with the present invention con to provide a refined chemical cellulose pulp which form to the generic formula has been treated with and retains a minor pro- R portion of certain soluble and stable morpholinium or thiomorpholinium derivatives. .X N 05. 3

It is a further object to provide an improved oral is viscose process for producing regenerated celluwherein, lose based on the use of such treated cellulose 7 pulp =a radical selectedfrom the group consisting The above and other objects will become more of oxygfmi 1 Sulfoxlde, and 511110115, apparent in the course of the following specifica- R=an allphailc hydrocarbon gmup contyammg tion and the appended claims. from 1 b0 24 carbon atoms, the three s may *ith viscose proc SS for preparing fil t be different hydrocarbon groups within said andn of regenerated cellulose-y refined chem limit, and the total number of carbon atoms in i'cai pulp is first converted to alkali cellulose by the three R S bemg from 8 to imm rsin th s ets of p in strong 1 s Compounds of this type can be prepared by the tion n l they a thoroughly s t r t d afte methods of Niederl and his associates as de- Which the excess of alkali is removed by b scribed, for example, in J. A. c. s. 63, 1476; as, ing the impregnated sheets to hydr lic pressure. 40 840; 67, 1227; 68, 714; 70, 618. The morpholine he al a cellulose is then Shredded to a fiuffy derivatives are preferably made from dichlorodifibrous condition and al owed o during ethyl ether, a primary aliphatic amine containwhichpe i d he product undergoes important ing a 6 to 24 carbon atom chain, and a dialkyl oxidativeproces'ses. The aged alkali cellulose is 1mm The thiomorpholine (also called t then converted. to Sodium Cellulose a e by morpholine) derivatives are preferably made by a' hqar disulfide and the Xanthate substituting dichloro-diethyl sulfide (mustard dissolved n dilute aqueous Sodium Y O e to gas) for the ether in the morpholine reaction, form visco e SO Q The Viscose SOIHfiOIl is while the sulfoxides and sulfones can be obtained owed to age or ripen for Several hours even by first oxidizing the mustard gas to the desired days underfcarefully controlled temperature cont t ditions during which time it is repeatedly filtered Examples of compounds of this group are to remove any undis ol fi t or ot er hexyl-methyl-morpholinium methosulfate; octylforei m t a clumps o ed, partiahy ethyl-morpholinium methosulfate; laurylr-methxanthated fibers. Finally the viscose is regeneryl morpholinium methosulfate; cetyl methyl ated into filaments or sheets by x rud g morpholinium methosulfate; lauryl -methyl-mor All of the compounds exhibit stability in strong alkaline media such as is employed in converting cellulose to alkali cellulose, in xanthating solution, in weaker alkaline media such as viscose solution, and in acid solution such as is employed in the coagulating or regenerating bath.

Because of their unique combination of stability, solubility in all of the viscose processing solution, and high substantivity for cellulose fibers the compounds herein described stay with the cellulose through all of the stages of viscose manufacture when incorporated with the refined cellulose pulp. When the cellulose is in solution to be filtered free of dust, gel clumps, and the like, the said compounds are not removed since they are soluble. expressed from cellulose fibers as in the preparation of alkali cellulose, the said compounds are strongly adsorbed on the cellulose fibers and the separated liquid is virtually free therefrom.

The presence of the morpholinium and thiomorpholinium compounds is beneficial in several of the steps of the viscose process and harmful in none of them; accordingly, I incorporate them with the cellulose at an early stage in the process, preferably during the course of preparing the cellulose pulp itself. Being surface active, the said compounds aid in the penetration of the fibrous masses of cellulose by the various treating solutions improving uniformity of reaction between the fibers and the said solutions. This has the indirect effect of improving the ease of filtration of the completed viscose solution because the number of suspended unreacted fibers and gel clumps of partially processed fibers is minimized. And, finally, the prevention of encrustation of extrusion orifices in the final regeneration step as taught in my hereinbefore mentioned application is effected.

In practicing the invention, a small proportion, as for example, from 0.01 to 0.2% of the surface active compound is incorporated with the cellulose in any suitable manner. In view of the hereinbefore disclosed tendency for the compounds of the invention to be strongly adsorbed by cellulose fibers the incorporation may conveniently be effected by dissolving the ap propriate amount of said compound in the water used in Washing the pulp subsequent to digestion of the wood chips in the sulfite process. Alternatively, relatively concentrated aqueous solutions of the said compounds may be sprayed on formed sheets of refined cellulose pulp after they have been partially dewatered but before they are dried.

When solution is being 95' Example I Inject into the stream of washing water in the washing of refined pulp a 10% aqueous solution of N -methyl-N-lauryl morpholinium methosulfate until one pound of such solution has been injected per hundred pounds of dry cellulose fiber in the batch being washed.

Example II Apply a uniform spray of a 20% aqueous solution of N-ethyl-N-cetyl-morpholinium ethosulfate to a wet web of refined cellulose pulp at the rate of 10 lbs. solution to lbs. of dry cellulose in the web and dry the said web.

The invention is not to be taken as limited to the specific illustrations given, but is of more general application as will be apparent to those skilled in the art. It should be pointed out that it is not essential to employ pure chemical compounds as the surface active addition agents, since equally valuable results are obtained using mixtures prepared by adding together difierent pure compounds of the class described, or mixtures occurring as the result of using mixed reactants (such as commercial grades of amines) in the manufacture of the morpholinium and/or thiomorpholinium derivatives. By way of example a preferred morpholinium compound for use in the present invention may be obtained by alkylating with diethyl sulfate the condensation product of dichlorodiethyl ether with a mixture of aliphatic amines containing approximately 10% hexadecylamine, 10% octadecyl amine, 35% octadecenyl amine, and 45% octadecadienyl amine. The said mixture of aliphatic amines is that obtained by converting the carboxyl (COOH) radical of soya acids to the aminomethyl (CH2NH2) radical (Armeen SD of Armour and Co.), and for convenience the morpholinium derivative may be termed N-ethyl-N- soya hydrocarbon-morpholinium ethosuliate.

What is claimed is:

1. As a composition of matter, refined cellulose pulp having incorporated therein a minor proportion of an N,N-dialiphatic-hydrocarbon-radical substituted morpholinium alkyl sulfate, wherein one of said hydrocarbon radicals contains from 12 to 18 carbon atoms and the other of said hydrocarbon radicals is an alkyl radical with not more than 2 carbon atoms, and. wherein the alkyl sulfate radical contains not more than 2 carbon atoms.

2. As a composition of matter, refined cellulose pulp having incorporated. therein a minor proportion of N-methyl-N-lauryl-morpholinium methosulfate.

3. As a composition of matter, refined cellulose pulp having incorporated therein a minor proportion of N-ethyl-N-cetyl-morpholinium ethosulfate.

4. As a composition of matter, refined cellulose pulp having incorporated therein a minor proportion of N-ethyl-N-soya-hydrocarbon-morpholinium ethosulfate.

5. As a composition of matter, refined cellulose pulp having incorporated therein from 0.01 to 0.2% of a compound as defined in claim 1.

6. As a composition of matter, refined cellulose pulp having incorporated therein from 0.01 to 0.2% of N -methyl N lauryl morpholinium methosulfate. V

7. As a composition of matter, refined cellulose pulp having incorporated therein from 0.01 to 0.2% of N-ethyl-N-cetyl-morpholinium ethosulfate.

' 8. As a composition of matter, refined cellulose pulp having incorporated therein from 0.01 to 0.2% or N-ethyl-N-soya. hydrocarbon-morpholinium ethosulfate.

9. In the viscose process for producing regenerated cellulose, the improvement which consists in introducing to the process, with the refined cellulose pulp and prior to conversion of the said pulp to alkali cellulose, a minor proportion, based on the said cellulose pulp of an N,N-di-aliphatichydrocarbon-radical substituted morpholinium alkyl sulfate, wherein one of said hydrocarbon radicals contains from 12 to 18 carbon atoms and the other of said hydrocarbon radicals is an alkyl radical with not more than 2 carbon atoms, and wherein the alkyl sulfate radical contains not more than 2 carbon atoms.

10. The process improvement of claim 9 wherein the said substituted morpholinium alkyl sulphate is N-methyl-Nlauryl-morpholinium methosulfate.

11. The process improvement of claim 9 wherein the said substituted morpholinium alkyl sulphate is N-ethyl-N-cetyl-morpholinium ethosulfate.

12. The process improvement of claim 9 wherein the said substituted morpholinium alkyl sulphate is N-ethyl-N-soya, hydrocarbon-morpholinium ethosulfate.

13. In the viscose process for producing regenerated cellulose the improvement which consists in introducing to the process with the refined cellulose pulp and prior to conversion of the said pulp to alkali cellulose, from 0.01 to 0.2%, based on the refined cellulose pulp, of N-methyl-N- lauryl-morpholinium methosulfate.

14. In the viscose process for producing regenerated cellulose the improvement Which consists in introducing to the process with the refined cellulose pulp and prior to conversion of the said pulp to alkali cellulose, from 0.01 to 0.2%, based on the refined cellulose pulp, of N-ethyl-N-cetylmorpholinium ethosulfate.

15. In the viscose process for producing regenerated cellulose the improvement which consists in introducing to the process with the refined cellulose pulp and prior to conversion of said pulp to alkali cellulose, from 0.01 to 0.2% based on the refined cellulose pulp, of N-ethyl-N-soya hydrocarbon-morpholinium ethosulfate.

KENNETH R. BROWN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,417,992 Niederl Mar. 22, 1947 2,432,127 Schlosser et al. Dec. 9, 1947 2,495,833 Brown Jan. 31, 1950 

1. AS A COMPOSITION OF MATTER, REFINED CELLULOSE PULP HAVING INCORPORATED THEREIN A MINOR PROPORTION OF AN N,N-DIALIPHATIC-HYDROCARBON-RADICAL SUBSTITUTED MORPHOLINIUM ALKYL SULFATE, WHEREIN ONE OF SAID HYDROCARBON RADICALS CONTAINS FROM 12 TO 18 CARBON ATOMS AND THE OTHER OF SAID HYDROCARBON RADICALS IS AN ALKYL RADICAL WITH NOT MORE THAN 2 CARBON ATOMS, AND WHEREIN THE ALKYL SULFATE RADICAL CONTAINS NOT MORE THAN 2 CARBON ATOMS. 